JP6499159B2 - Copper alloy wire and method for producing the same - Google Patents

Description

  The present invention relates to a copper alloy wire and a method for producing the same, and more particularly to an ultrafine copper alloy wire for a magnet wire and a method for producing the same.

  With the development of electronic devices, electronic components have been downsized, and the demand for extra fine copper alloy wires having a wire diameter of 0.1 mm or less has increased. For example, a coil for a microspeaker used in a mobile phone, a smartphone, or the like is manufactured by winding an extra fine wire (magnet wire) having a wire diameter of 0.1 mm or less into a coil shape.

  Since this winding process requires toughness (elongation) that enables the formation of turns, pure copper having excellent toughness has been used. However, pure copper is excellent in conductivity but low in strength. In addition, there is a problem that the coil life is short because the fatigue resistance associated with coil vibration is low. Furthermore, the improvement of the coil moldability which can be coil-wound from a long copper alloy wire is required. In particular, in the case of a small coil or a square coil, the processing becomes more severe, and thus high coil formability and elongation are required. In addition, when processing a wire material with a thin wire diameter into a coil shape, high elongation is required, but there is a dilemma that elongation becomes difficult to occur as the wire diameter becomes thinner.

  In order to solve this problem, a high-concentration Cu-Ag alloy containing 2 to 15% by mass of Ag that can increase the tensile strength without decreasing the conductivity is adjusted, and the workability of the final processing is adjusted. It has been proposed to achieve both elongation and strength (Patent Document 1). In general, a processed metal or alloy has an increased tensile strength and a reduced elongation. However, when a heat treatment at a certain temperature or higher is applied thereto, the elongation is restored and the strength is decreased. Thus, it has been proposed that both the strength and elongation be achieved even in a low-concentration alloy by performing the heat treatment temperature below the softening temperature (Patent Document 2). However, this method is difficult to control the heat treatment temperature and time. Therefore, by adding 0.05 to 0.2% by mass of Ag and 0.003 to 0.01% by mass of Zr to the copper, the semi-softening temperature range is widened, and the semi-softening treatment achieves both strength and elongation. A technique for performing the above has been proposed (Patent Document 3).

JP 2009-280860 A Japanese Patent No. 3944304 Japanese Patent Publication No. 4-77060

  However, along with demands for longer life and ultrafine magnet wires (for example, wire diameters of 0.07 mm or less), there is a demand for both high strength and improved elongation of copper alloy wires. In addition, further improvements in coil winding workability and bending fatigue resistance are required. Bending fatigue resistance is one measure of coil life.

  The method described in Patent Document 1 is for high-cost alloys containing high concentrations of Ag up to 2-15%. For this reason, there is a need for a technique that can exhibit sufficient strength and elongation even with a lower concentration of Cu—Ag alloy or a copper alloy that does not contain Ag. Moreover, as described in Patent Document 1, when the Ag content is increased in order to increase the strength, on the other hand, the conductivity is lowered. Furthermore, Ag is an element that improves heat resistance, and heat treatment becomes difficult. In addition, when processing up to an ultrathin line, it may not be possible to obtain sufficient characteristics just by adjusting the final processing degree.

  A general solid solution type highly conductive copper alloy as described in Patent Document 2 has a narrow temperature range for realizing a semi-softening heat treatment. For this reason, it is difficult to realize stable performance. Further, it is difficult to further increase the strength and improve the bending fatigue resistance while securing the conductivity and elongation with the copper alloy described in Patent Document 2. In addition, since the elongation of the wire obtained by the semi-softening heat treatment is lower than the elongation of the wire obtained by the softening treatment, the formability of the wire obtained by the semi-softening heat treatment is suitable for coil winding processing under more severe conditions. It is insufficient for this.

  Furthermore, the method of adding a small amount of Zr to a low-concentration Cu—Ag alloy and performing a semi-softening treatment (Patent Document 3) can easily achieve both elongation and strength. In terms of elongation, it was insufficient. Recently, the shape of the magnet wire is not limited to a round wire, and the use of a square wire or a flat wire is also being studied. Also in the case of these square wires and flat wires, it is required that the wire be thin enough to correspond to the diameter of the round wire.

  The present invention has been made in view of the problems in the prior art, and has high elongation and excellent workability, that is, coil formability. In addition, the characteristics of the coil obtained using the copper alloy wire An object is to provide a copper alloy wire excellent in (coil life), for example, used for a magnet wire or the like at low cost.

  In order to develop a copper alloy wire having high elongation, excellent workability, and excellent coil characteristics (coil life) obtained by using the copper alloy wire, the present inventors have developed various copper alloys. The inventors studied diligently about the alloy and its manufacturing method. As a result, it was found that by properly controlling the recrystallized texture of the copper alloy wire, a copper alloy wire having high elongation, excellent coil formability, and excellent coil characteristics (coil life) can be obtained. . The present invention has been completed based on this finding.

That is, according to the present invention, the following means are provided.
(1) A copper alloy wire containing 0.1 to 4.0% by mass of Ag with the balance being Cu and inevitable impurities,
Copper alloy whose area ratio of crystal grains having <101> orientation is 10% or more and 40% or less of the total measured area when a cross section perpendicular to the longitudinal direction of the wire is observed by the EBSD method from the normal direction of the cross section wire.
(2) 0.1 to 4.0% by mass of Ag, and 0.05 as each content of at least one selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr A copper alloy wire containing ~ 0.30 mass% with the balance being Cu and inevitable impurities,
Copper alloy whose area ratio of crystal grains having <101> orientation is 10% or more and 40% or less of the total measured area when a cross section perpendicular to the longitudinal direction of the wire is observed by the EBSD method from the normal direction of the cross section wire.
(3) At least one selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr is contained in an amount of 0.05 to 0.30% by mass, and the balance is inevitable with Cu. A copper alloy wire made of mechanical impurities,
Copper alloy whose area ratio of crystal grains having <101> orientation is 10% or more and 40% or less of the total measured area when a cross section perpendicular to the longitudinal direction of the wire is observed by the EBSD method from the normal direction of the cross section wire.
(4) The copper alloy wire according to any one of (1) to (3), wherein an area ratio of crystal grains having the <101> orientation is 20% or more and 40% or less of a total measurement area.
(5) The copper alloy wire according to any one of (1) to (4), wherein the base material has an average crystal grain size of 0.2 to 5.0 μm.
(6) A step of obtaining a rough drawn wire by melting and casting a copper alloy material containing 0.1 to 4.0% by mass of Ag and the balance being an alloy composition of Cu and inevitable impurities;
A process of obtaining a wire having a predetermined wire diameter by repeating cold working and intermediate annealing at a working degree η of 0.5 or more and 4 or less at least once in this order on the rough drawn wire;
Thereafter, the wire has a process of performing a final cold working and a final annealing in this order with a working degree η of 0.5 or more and 4 or less,
The intermediate annealing and the final annealing are both at 400 to 800 ° C. under an inert gas atmosphere if done in batch, and the recrystallization temperature or more on the 30 minutes to 2 hours of the copper alloy material, or, If carried out in continuous mode at 500 to 850 ° C. under an inert gas atmosphere, and a heat treatment of 0.1 to 5 seconds on the recrystallization temperature or more of the copper alloy material, a copper alloy according to (1) claim A manufacturing method of a wire.
(7) 0.1 to 4.0% by mass of Ag, and at least one selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr is 0.05 as each content A step of obtaining a rough drawn wire by melting and casting a copper alloy material containing ~ 0.30% by mass and the balance being an alloy composition consisting of Cu and inevitable impurities;
A process of obtaining a wire having a predetermined wire diameter by repeating cold working and intermediate annealing at a working degree η of 0.5 or more and 4 or less at least once in this order on the rough drawn wire;
Thereafter, the wire has a process of performing a final cold working and a final annealing in this order with a working degree η of 0.5 or more and 4 or less,
The intermediate annealing and the final annealing are both at 400 to 800 ° C. under an inert gas atmosphere if done in batch, and the recrystallization temperature or more on the 30 minutes to 2 hours of the copper alloy material, or, If carried out in continuous mode at 500 to 850 ° C. under an inert gas atmosphere, and a heat treatment of 0.1 to 5 seconds on the recrystallization temperature or more of the copper alloy material, a copper alloy according to item (2) A manufacturing method of a wire.
(8) At least one selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr is contained in an amount of 0.05 to 0.30% by mass, and the balance is inevitable with Cu. A step of melting and casting a copper alloy material that gives an alloy composition consisting of mechanical impurities to obtain a rough drawn line;
A process of obtaining a wire having a predetermined wire diameter by repeating cold working and intermediate annealing at a working degree η of 0.5 or more and 4 or less at least once in this order on the rough drawn wire;
Thereafter, the wire has a process of performing a final cold working and a final annealing in this order with a working degree η of 0.5 or more and 4 or less,
The intermediate annealing and the final annealing are both performed at 300 to 800 ° C. or 400 to 800 ° C. in the case of containing Zr in an inert gas atmosphere when performed in a batch mode , and in any case, the copper alloy material. recrystallization temperature than the 30 minutes to 2 hours, or, if performed in a continuous mode at 500 to 850 ° C. If containing 400 to 850 ° C. or Zr in an inert gas atmosphere, and the both cases a heat treatment of 0.1 to 5 seconds on the recrystallization temperature or more of the copper alloy material, (3) the method of producing a copper alloy wire according to claim.

  In the present invention, the wire means a square wire or a flat wire in addition to the round wire. Accordingly, the wire of the present invention refers to a round wire, a square wire, and a flat wire unless otherwise specified. Here, the size of the wire means that the wire diameter φ (diameter of the circle of the cross section) of the round wire is a square wire (in the wire drawing direction) if the wire is a round wire (a cross section perpendicular to the wire drawing direction is circular). If the cross section perpendicular to the square is square, the thickness t and width w of the square wire (both are the length of one side of the square of the cross section and have the same value) are converted into rectangular wires (drawing direction). Is the thickness t (the length of the short side of the rectangle of the cross section) and the width w (the length of the long side of the rectangle of the cross section).

According to the present invention, the balance between the predetermined strength required for coil forming and good elongation is excellent, and in addition to this, the characteristics of the coil obtained by using the copper alloy wire (specifically, bending fatigue resistance) It is possible to obtain a copper alloy wire excellent in coil life expressed by characteristics and coil formability that can form a long copper alloy wire into a coil with few defects. The copper alloy wire of the present invention can be suitably used for, for example, a magnet wire. Moreover, according to the manufacturing method of the copper alloy wire of this invention, the said copper alloy wire can be manufactured stably cheaply.
The above and other features and advantages of the present invention will become more apparent from the following description, with reference where appropriate to the accompanying drawings.

FIG. 1 is a schematic diagram showing changes in strength and elongation of a copper alloy wire with respect to changes in heat treatment temperature. In FIG. 1, the example in the copper alloy composition of Example 52 was shown. FIG. 2 is a front view schematically showing an apparatus used in a test for measuring the number of bending fatigue fractures (number of repetitions until fracture) performed in the examples.

  Hereinafter, the present invention will be described in more detail.

[Alloy composition]
The copper alloy wire of the present invention contains 0.1 to 4% by mass of Ag and / or at least one selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr. The content is preferably 0.05 to 0.30% by mass, and the balance consists of Cu and inevitable impurities. Here, when the content of the alloy additive element is simply “%”, it means “mass%”. Further, there is no particular limitation on the total content of at least one alloy component selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr, but the conductivity of the copper alloy wire is significantly reduced. In order to prevent this, the total content of at least one alloy component selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr other than Ag is preferably 0.50% by mass or less. More preferably, it is 0.05-0.30 mass%.

  In the copper alloy wire of the present invention, in addition to Cu and inevitable impurities, [1] Ag may be contained alone, or [2] from Sn, Mg, Zn, In, Ni, Co, Zr and Cr. Or at least one selected from the group consisting of [3] these [1] Ag and [2] group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr You may contain both at least 1 sort (s) chosen from.

These elements are solid solution strengthening type or precipitation strengthening type elements, respectively, and by adding these elements to Cu, the strength can be increased without significantly reducing the conductivity.
This addition increases the strength of the copper alloy wire itself and improves the bending fatigue resistance. In general, the bending fatigue resistance is proportional to the tensile strength, but if processing is performed in order to increase the tensile strength, the elongation decreases and it becomes impossible to form into an ultrafine copper alloy wire such as a magnet wire. Here, the bending strain applied to the copper alloy wire during bending fatigue is larger at the outer peripheral portion of the wire, and the bending strain is smaller as it is closer to the center portion. According to this invention, the whole wire is maintaining the softened state. For this reason, since the elongation as a whole wire can be secured sufficiently, it becomes possible to form an ultrafine copper alloy wire such as a magnet wire.

Among these elements, Ag is an element that can increase the strength without lowering the conductivity, and a Cu-Ag alloy is suitable as the copper alloy according to the present invention used for, for example, a magnet wire. Ag is an example of an essential additive element in the copper alloy according to the present invention. In the present invention, the Ag content is 0.1 to 4.0%, preferably 0.5 to 2.0%. If the Ag content is too low, sufficient strength cannot be obtained. Moreover, when there is too much Ag content, while electroconductivity will fall, cost will become high too much.
In addition, when Ag content is less than 0.1 mass%, it is regarded as an inevitable impurity.

At least one element selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr is another example of the essential additive element in the copper alloy according to the present invention. In the present invention, the content of these elements is preferably 0.05 to 0.30% by mass, and more preferably 0.05 to 0.20% by mass, as each content. When this content is too small as each content, the effect of the strength increase by addition of these elements is hardly expected. Moreover, when there is too much this content, the fall of electrical conductivity is too large and it is unsuitable as copper alloy wires, such as a magnet wire.
When at least one element selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr is less than 0.05% by mass, it is regarded as an inevitable impurity.

[Crystal orientation]
The copper alloy wire of the present invention is characterized in that the <101> texture is 10% or more of the whole. The <101> texture is preferably 20% or more of the whole. Here, when <101> the texture is 10% or more of the whole, when a cross section perpendicular to the longitudinal direction (drawing direction) of the wire is observed from the normal direction of the cross section by the EBSD method, <101 > The area ratio of crystal grains having an orientation is 10% or more of the total measurement area. When a copper alloy wire is subjected to drawing and heat treatment under normal conditions, a <100> texture and a <111> texture develop. However, as a result of repeated studies on copper alloy ultrafine wires having various structures, the present inventors have found that <101> a copper alloy wire satisfying a texture of 10% or more of the entire structure has excellent elongation and excellent coil formability. It has been found that it exhibits its characteristics. In addition, if there are too many <101> textures, the strength may be insufficient. Therefore, the <101> texture is preferably 40% or less of the total.

[EBSD method]
The EBSD method is used for the observation and analysis of the crystal orientation in the present invention. EBSD is an abbreviation for Electron BackScatter Diffraction, and is a crystal orientation analysis technique using reflected electron Kikuchi line diffraction that occurs when a sample is irradiated with an electron beam in a scanning electron microscope (SEM).

  In the EBSD measurement in the present invention, the section (transverse section) perpendicular to the longitudinal direction of the wire is scanned at 0.02 μm steps to analyze the orientation of each crystal grain. As a result of the analysis, a surface whose deviation angle from the <101> orientation is within ± 10 degrees is defined as a <101> surface, and a cross section perpendicular to the longitudinal direction of the wire is observed by the EBSD method from the normal direction of the cross section In this case, a crystal grain having a plane whose deviation angle from the <101> orientation is within ± 10 degrees is defined as a crystal grain having a <101> orientation. Then, when a cross section perpendicular to the longitudinal direction of the wire is observed by the EBSD method from the normal direction of the cross section, the ratio of the area of the crystal grains having the <101> orientation has the <101> orientation. The area ratio (%) of crystal grains is obtained. What is necessary is just to determine the said scanning step suitably according to the magnitude | size of the crystal grain of a sample. For the analysis of the crystal grains after the measurement, for example, analysis software OIM software (trade name) manufactured by TSL Solution can be used. Information obtained in the analysis of crystal grains by EBSD measurement includes information up to a depth of several tens of nanometers in which the electron beam penetrates the sample, but is sufficiently small with respect to the measured width. In the inside, it treats as an area ratio of a crystal grain. In addition, since the area of the crystal grains differs in the longitudinal direction (LD) of the wire, it is preferable to average some points in the longitudinal direction.

[Average crystal grain size of base material of copper alloy wire]
In order to further improve the characteristics in the present invention, the average crystal grain size is preferably 0.2 to 5.0 μm. When the average crystal grain size is too small, since the crystal grains are excessively fine, the work hardening ability is lowered, and the elongation may be slightly lowered. On the other hand, when the average crystal grain size is too large, non-uniform deformation is likely to occur, and elongation may decrease.

[Production method]
The manufacturing method of the copper alloy wire of the present invention will be described.
As described above, the shape of the copper alloy wire of the present invention is not limited to a round wire, and may be a square wire or a flat wire, which will be described below. In addition, the copper alloy wire of the present invention is not a processed finish but an annealed finish.

[Manufacturing method of round wire]
First, the copper alloy round wire manufacturing method of the present invention includes, for example, casting, cold working (specifically, cold wire drawing, also called intermediate cold working), intermediate annealing, and final cold working. And each step of final annealing. Here, cold working and intermediate annealing may be performed in this order as necessary, and these processes may be repeated twice or more in this order. The number of repetitions of cold working and intermediate annealing is not particularly limited, but is usually 1 to 5 times, preferably 2 to 4 times. When the ingot size is close to the final wire diameter (for example, when the degree of processing from the ingot to the final wire diameter is in the range of 0.5 to 4, that is, when the ingot size is small or the final wire diameter is large) It can be omitted without necessarily requiring intermediate annealing. In this case, cold working as intermediate wire drawing after intermediate annealing is also omitted.

[casting]
In a crucible, the additive elements of Cu and Ag, Sn, Mg, Zn, In, Ni, Co, Zr, and Cr are melted and cast. The atmosphere of the crucible when melting is preferably an atmosphere of an inert gas such as a vacuum or nitrogen or argon in order to prevent formation of oxides. There is no restriction | limiting in particular in a casting method, For example, the continuous casting wire drawing methods, such as a horizontal type continuous casting machine and an Upcast method, can be used. According to these continuous casting wire drawing methods, rough drawing wire having a diameter of about 8 to 23 mm is usually obtained by continuously performing the steps from casting to wire drawing. On the other hand, when not using the continuous casting wire drawing method, a roughing wire having a diameter of about 8 to 23 mm is similarly obtained by subjecting a billet (ingot) obtained by casting to wire drawing.

[Cold working, intermediate annealing]
You may perform cold processing and heat processing (intermediate annealing) with respect to this rough drawing wire at least once in this order as needed. By performing these cold working and heat treatment (intermediate annealing), a thin wire having a diameter of usually about 0.06 to 1 mm is obtained.

The working degree and working rate in each cold working will be described.
Each cold working is performed so as to obtain a wire (thin diameter wire) within a range of a working degree (η) of 0.5 or more and 4 or less. Here, the processing degree (η) is defined by η = ln (S ₀ / S ₁ ), where S _{0 is} the cross-sectional area of the wire before processing and S ₁ is the cross-sectional area of the wire after processing. If this degree of processing is too small, strength and elongation are not sufficiently expressed by heat treatment (intermediate annealing) after processing, and since the number of steps increases, the amount of energy consumption increases, and thus the production efficiency is poor. Absent. If the degree of processing is too high, the orientation of the <101> texture (area ratio of the crystal grains having the <101> orientation) is less than 10%, and instead the <111> texture is It increases and affects the structure after finish annealing (final annealing), and the elongation becomes low.

  Here, each cold working may be performed by a plurality of cold working passes. The number of cold working passes between two consecutive heat treatments (intermediate annealing) is not particularly limited, but is usually 2 to 40 times.

  In the manufacturing method disclosed in Patent Document 1, only the degree of processing in the processing before the final heat treatment is adjusted. On the other hand, in the manufacturing method of the present invention, as cold working between each two heat treatment steps, in each intermediate cold drawing (intermediate cold working) and finish cold drawing (final cold working). By properly controlling the degree of processing, the orientation of the recrystallized texture can be controlled appropriately, the strength and elongation are balanced and high, and the copper alloy wire has excellent coil characteristics. can do.

  After each cold working, intermediate annealing is performed as necessary. As described above, intermediate annealing may be omitted when the ingot size is close to the final wire diameter. Although the specific heat treatment temperature differs depending on the alloy composition, the intermediate annealing needs to be performed at a temperature higher than the recrystallization temperature. Copper alloy wires are roughly classified into two types of crystal structure states. One is a processed structure. This is a structure state in which many strains are introduced into the crystal by wire drawing or the like. The other is a recrystallized structure. This is a textured state with little variation in crystal grain size and relatively little distortion.

  By performing an intermediate annealing with a certain amount of heat, the processed structure of the copper alloy wire changes to a recrystallized structure. In the present invention, a temperature at which almost all of the metal structure is changed to a recrystallized structure is defined as a “recrystallization temperature”. A heat treatment (temperature / time) that changes almost all of the metal structure to a recrystallized structure is called a softening process. The temperature and time of the softening process vary depending on the composition, processing degree, thermal history, etc. of the copper alloy wire. In particular, it is known that a copper alloy wire added with Ag or Zr has a high recrystallization temperature. The greater the degree of processing, the softer the treatment becomes even at lower temperatures. Also, the longer the heat treatment time that has already passed, the softening heat treatment becomes possible even at lower temperatures. When the temperature of the softening treatment is increased, recrystallization further proceeds, the elongation of the copper alloy wire is recovered, and the strength is lowered. However, in general, the recovery of elongation and the decrease in strength reach an inflection point at the recrystallization temperature. In terms of material properties, heat treatment above this inflection point is called softening treatment. In other words, in general, the heat treatment at a temperature below the recrystallization temperature up to the vicinity of the recrystallization temperature has a large elongation and change in strength with respect to the change in the heat treatment temperature, but the heat treatment temperature at a temperature higher than the recrystallization temperature. The change in elongation and strength with respect to the change is small.

  When heat treatment at a temperature higher than the recrystallization temperature is performed, the structure is rearranged into the recrystallized structure and the strain is eliminated, so that the strength decreases and the elongation improves (recovers). However, even when heat treatment is performed at a temperature lower than the recrystallization temperature, recovery (rearrangement of dislocations) and partial recrystallization occur, and recovery of elongation and a decrease in strength begin to occur. In the present invention, a heat treatment is performed for a predetermined time in a temperature range from a temperature at which the recovery of elongation and a decrease in strength occur (temperature exceeding about 200 ° C. in the example shown in FIG. 1) to below the recrystallization temperature (less than 500 ° C.). Is called semi-softening treatment. Since the heat treatment is performed at a temperature lower than the recrystallization temperature, the semi-softened structure is a structure in which a processed structure and a recrystallized structure are mixed. The temperature range of the semi-softening heat treatment also varies depending on the alloy composition, the amount of deformation, the thermal history, etc., as in the softening treatment.

  As a reference, the relationship between the annealing temperature, strength, and elongation in the copper alloy composition of Example 52 is shown in FIG. In this example, the recrystallization temperature or softening temperature is 500 ° C. Thus, softening treatment and semi-softening treatment are distinguished as treatments that give different physical properties to the copper alloy wire. The intermediate annealing in the method for producing a copper alloy wire according to the present invention corresponds to “softening treatment”. Therefore, the heat treatment temperature is higher than the recrystallization temperature.

The heat treatment method for performing the intermediate annealing is roughly classified into a batch type and a continuous type.
Batch-type heat treatment is inferior in productivity because it takes processing time and cost, but it is easy to control characteristics because temperature and holding time are easy to control. In contrast, continuous heat treatment is excellent in productivity because it can be heat treated continuously with the wire drawing process, but since heat treatment needs to be performed in an extremely short time, the heat treatment temperature and time are accurately controlled to stabilize the characteristics. It is necessary to realize this. Since each heat treatment method has advantages and disadvantages as described above, a heat treatment method according to the purpose is selected. In general, the heat treatment is performed in a shorter time as the heat treatment temperature is higher, and the heat treatment is performed in a longer time as the heat treatment temperature is lower.

  When performing the intermediate annealing in a batch system, for example, heat treatment is performed at 300 to 800 ° C. for 30 minutes to 2 hours in a heat treatment furnace in an inert gas atmosphere such as nitrogen or argon. In particular, when an element for improving heat resistance such as Ag or Zr is added, it is preferable to perform heat treatment at 400 to 800 ° C. for 30 minutes to 2 hours. As described above, the specific heat treatment temperature varies depending on the alloy composition, but the intermediate annealing temperature is equal to or higher than the recrystallization temperature. Hereinafter, the intermediate annealing performed in batch mode is also abbreviated as batch annealing.

On the other hand, examples of the continuous heat treatment include an electric heating method and an in-atmosphere heat treatment method.
First, the electric heating method is a method in which an electrode ring is provided in the middle of the wire drawing process, a current is passed through the copper alloy wire passing between the electrode wheels, and heat treatment is performed by Joule heat generated in the copper alloy wire itself.
Next, the in-atmosphere running heat treatment method is a method in which a heating container is provided in the middle of wire drawing, and a copper alloy wire is passed through the heating container atmosphere heated to a predetermined temperature to perform heat treatment.
Any of the heat treatment methods is preferably performed in an inert gas atmosphere in order to prevent oxidation of the copper alloy wire.

The heat treatment conditions when the intermediate annealing is performed continuously are preferably performed at 400 to 850 ° C. for 0.1 to 5 seconds. In particular, when an element that enhances heat resistance such as Ag or Zr is added, it is preferable to perform heat treatment at 500 to 850 ° C. for 0.1 to 5 seconds. As described above, the specific heat treatment temperature varies depending on the alloy composition, but the intermediate annealing temperature is equal to or higher than the recrystallization temperature.
Hereinafter, the intermediate annealing performed by the two types of continuous heat treatment of the energization heating method and the in-atmosphere running heat treatment method will be abbreviated as current annealing and running annealing, respectively. If the intermediate annealing by any one of these heat treatments is insufficient, sufficient strain removal and recrystallization cannot be performed and the <111> processed texture remains, so that the final product has sufficient elongation. It cannot be expressed.

[Finishing cold working (final cold working)]
If necessary, finish cold working is performed on the wire subjected to the cold working and intermediate annealing to obtain a desired wire diameter. This finish cold work is also performed within the range in which the degree of work (η) of the copper alloy wire is 0.5 or more and 4 or less, similar to the intermediate cold work. When the degree of work is too small, sufficient work cannot be given, so that the work hardening of the copper alloy wire becomes insufficient, and the strength of the copper alloy wire obtained after finish annealing (final annealing) becomes insufficient. On the other hand, if the degree of work is too large, <101> texture cannot be obtained 10% or more after finish annealing, and sufficient elongation cannot be obtained. Preferably, the finish cold working is performed within a range where the degree of work is 0.5 or more and 3 or less, and more preferably, the finish cold work is performed within a range where the degree of work (η) is 0.5 or more and 2 or less. Do. By performing finish cold working at this preferred degree of work, it is possible to obtain a superior copper alloy wire having a <101> texture of 10% or more and an elongation of 25% or more.

[Finish annealing (final annealing)]
The copper alloy wire that has been drawn to a desired size in the finish cold working (final cold working) step is subjected to finish annealing at a recrystallization temperature or higher as the final heat treatment. This heat treatment is also equivalent to the softening treatment. When finishing annealing is performed batchwise, heat treatment is performed at 300 to 800 ° C. for 30 minutes to 2 hours. On the other hand, when finishing annealing is performed continuously, heat treatment is performed at 400 to 850 ° C. for 0.1 to 5 seconds. In particular, when an element for improving heat resistance such as Ag and Zr is added, heat treatment is performed at 400 to 800 ° C. for 30 minutes to 2 hours in the case of a batch type, while 0 to 500 to 850 ° C. in the case of a continuous type. Perform heat treatment for 1 to 5 seconds. As described above, the specific heat treatment temperature varies depending on the alloy composition, but the finish annealing temperature is equal to or higher than the recrystallization temperature.

Hereinafter, finish annealing performed in batch mode is also abbreviated as batch annealing. Moreover, the finish annealing performed by the two types of continuous methods is also abbreviated as current annealing and running annealing, respectively.
The heat treatment for the finish annealing is preferably at or above the recrystallization temperature (recrystallization temperature + 200 ° C.) or less, more preferably at or above the recrystallization temperature (recrystallization temperature + 100 ° C.) or less, more preferably at or above the recrystallization temperature (recrystallization temperature). (Crystal temperature + 50 ° C.) or less. If the temperature of the final heat treatment (final annealing) is too high, the strength decreases. Furthermore, if the heat treatment is performed at a temperature higher than (recrystallization temperature + 200 ° C.), the crystal grains become coarse and elongation decreases.

[Manufacturing method of flat wire]
Next, the manufacturing method of the copper alloy rectangular wire of the present invention is the same as the manufacturing method of the round wire, except that it has a rectangular wire processing step. Specifically, the method for producing a copper alloy flat wire of the present invention includes, for example, casting, cold working (cold drawing), flat wire working, and final heat treatment (final annealing) in this order. . If necessary, intermediate annealing (intermediate heat treatment) may be inserted between the cold working and the rectangular wire working, as in the method for producing the round wire. The conditions of processing and heat treatment in each step of casting, cold working, intermediate annealing, and final annealing, and preferable conditions thereof, and the number of repetitions of cold working and intermediate annealing are the same as in the method of manufacturing the round wire.

[Square wire processing]
Before flat wire processing, in the same way as the manufacture of round wire, cold work (drawing) is performed on the ingot obtained by casting to obtain a round wire-shaped rough drawing wire, and if necessary, intermediate annealing is performed. Apply. As the flat wire processing, the round wire (rough drawing wire) thus obtained is subjected to cold rolling with a rolling mill, cold rolling with a cassette roller die, pressing, drawing processing, and the like. By this flat wire processing, the cross-sectional shape in the width direction (TD) is processed into a rectangular shape to obtain a flat wire shape. This rolling or the like is usually performed by 1 to 5 passes. The rolling reduction and the total rolling reduction in each pass during rolling or the like are not particularly limited, and may be set as appropriate so that a desired rectangular wire size can be obtained. Here, the rolling reduction is the rate of change in thickness in the rolling direction when rectangular wire processing is performed. When the thickness before rolling is t ₁ and the thickness after rolling is t ₂ , the rolling reduction ( %) Is represented by {1- (t ₂ / t ₁ )} × 100. In the present invention, the processing degree η in rectangular wire processing is defined as η = ln (t ₁ / t ₂ ). For example, the total rolling reduction can be 10 to 90%, and the rolling reduction in each pass can be 10 to 50%. Here, in the present invention, the cross-sectional shape of the rectangular wire is not particularly limited, but the aspect ratio is usually 1 to 50, preferably 1 to 20, and more preferably 2 to 10. The aspect ratio (expressed as w / t below) is the ratio of the long side to the short side of the rectangle that forms the width direction (TD) cross section (ie, the cross section perpendicular to the longitudinal direction) of the flat wire. As for the size of the flat wire, the thickness t of the flat wire is equal to the short side of the rectangle forming the width direction (TD) cross section, and the width w of the flat wire is the length of the rectangle forming the cross section of the width direction (TD). Equal to edge. The thickness t of the flat wire is usually 0.1 mm or less, preferably 0.07 mm or less, more preferably 0.05 mm or less. The width w of the flat wire is usually 1 mm or less, preferably 0.7 mm or less, more preferably 0.5 mm or less.
When this rectangular wire is wound in the thickness direction, high tensile strength, elongation, and electrical conductivity can be expressed as in the case of the round wire according to the present invention. Here, winding a flat wire in the thickness direction means winding the flat wire in a coil shape with the width w of the flat wire being the width of the coil.

[Manufacturing method of square wire]
Furthermore, when manufacturing a square wire, what is necessary is just to set so that the width direction (TD) cross section may become a square (w = t) in the manufacturing method of the said flat wire.

[Another Embodiment of Flat Wire and Square Wire Manufacturing Method]
Instead of the above manufacturing method, a plate material or strip material having a predetermined alloy composition can be manufactured, and these plates or strips can be slit to obtain a rectangular wire material or a rectangular wire material having a desired line width.
As this manufacturing process, for example, there is a method comprising casting, hot rolling, cold rolling, finish annealing, and slit processing. If necessary, intermediate annealing may be performed during the cold rolling. In some cases, the slit processing may be performed before the finish annealing.

[Physical properties]
By the production method of the present invention described above, a copper alloy wire having a <101> structure area ratio of 10% or more, preferably 20% or more (usually 40% or less) can be obtained. The copper alloy wire of the present invention preferably has a tensile strength of 260 MPa or more, more preferably 300 MPa or more. If the tensile strength is too small, the strength when the diameter is reduced is insufficient, and the bending fatigue resistance may be inferior. Although there is no restriction | limiting in particular in the upper limit of tensile strength, Usually, it is 400 Mpa or less. Moreover, the copper alloy wire of the present invention preferably has an elongation (tensile elongation at break) of 20% or more, more preferably 30% or more. If the elongation is too small, problems such as breakage may occur when the coil is formed. Although there is no restriction | limiting in particular in the upper limit of elongation, Usually, it is 40% or less.

  The copper alloy wire of the present invention preferably has a conductivity of 70% IACS or more, more preferably 80% IACS or more, and still more preferably 90% IACS or more. Higher conductivity is preferable as a magnet wire, for example, because energy loss is lower. The conductivity of the magnet wire is required to be 70% IACS or more, preferably 80% IACS or more, and more preferably 90% IACS or more. Although there is no restriction | limiting in particular in the upper limit of electrical conductivity, Usually, it is below 100% IACS.

  The copper alloy wire of the present invention preferably exhibits high bending fatigue resistance while having high elongation that can be formed as an ultrafine magnet wire. Moreover, the copper alloy wire of the present invention is preferably excellent in coil characteristics (coil life, coil formability). Furthermore, the copper alloy wire of the present invention preferably has a high electrical conductivity.

[Wire diameter or wire thickness, application]
Although there is no restriction | limiting in particular in the wire diameter of the copper alloy wire of this invention, or the thickness of a wire, Preferably it is 0.1 mm or less, More preferably, it is 0.07 mm or less, More preferably, it is 0.05 mm or less. The lower limit of the wire diameter or the wire thickness is not particularly limited, but is usually 0.01 mm or more in the current technology.
The use of the copper alloy wire of the present invention is not particularly limited, and examples thereof include a magnet wire that is an extra fine wire used for a speaker coil used in a mobile phone, a smartphone, and the like.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[Examples of round wires, comparative examples]
The cast material is made of 0.1 to 4% by mass of Ag and / or 0.05 to 0.3% by mass of Sn, Mg, Zn, In, Ni, Co, Zr, and Cr as each content. A book having various alloy compositions shown in Tables 1-1, 2-1, 2-6, 2-11, 4-1, which contains at least one selected from the group, and the balance consisting of Cu and inevitable impurities The copper alloy material of the invention example (Example) and the copper alloy material of the comparative example having various alloy compositions shown in Tables 1-1, 2-1, 2-6, 2-11, 4-1, Each was cast into an ingot (rough drawing wire) having a diameter of 8 to 22 mm by a horizontal continuous casting method.
The rough drawing wire is subjected to cold working (intermediate cold drawing), intermediate annealing (intermediate heat treatment), final cold working (finish cold drawing) and final annealing (finish heat treatment) in this order, Each round wire sample (test material) of the various wire diameters shown was created.
The heat treatment of intermediate annealing and final annealing was performed by any one method selected from three patterns of batch annealing, current annealing, and running annealing, and all were performed in a nitrogen atmosphere. In each table, the method of heat treatment performed is indicated as “batch”, “current”, and “running”. The heat treatment temperature and heat treatment time of the heat treatment are shown in each column. The intermediate annealing and the final annealing are shown in the order of heat treatment 1 → heat treatment 2 → heat treatment 3 →. “X” shown as “heat treatment X” indicates the order (number) of the number of times (Xth) annealing. Of these, the last heat treatment is final annealing. In the test examples shown in each table, there are a case where intermediate annealing is performed once to four times and a case where intermediate annealing is not performed once. In each test example, the value shown in the “wire diameter” column in the “heat treatment X” section is the value of the wire after the cold working (intermediate cold working or final cold working) immediately before the X-th heat treatment. The wire diameter. The degree of work in this cold work (intermediate cold work or final cold work) is shown in the “work degree” column.
In Tables 1-2, 2-4, 2-9, and 2-14, the degree of working in the final cold working (final cold working) is shown in the column of “Degree of working in final working”. .

[Examples of rectangular wires, comparative examples]
Using the copper alloys of the present invention examples (examples) having various alloy compositions shown in Table 3-1 and the copper alloy of the comparative example, the same as the round wire, except that the ingot was cold worked. After subjecting the rough drawn wire obtained by (drawing) to intermediate annealing (heat treatment 1 in the table), at least one cold working (drawing) and intermediate annealing (heat treatment 2 → heat treatment 3 in the table → After being subjected to the heat treatment 4), a rectangular wire was processed, and then finish annealing (any one of heat treatment 3, heat treatment 4, and heat treatment 5 in the table) was performed to produce a rectangular wire sample.
As shown in Tables 3-3 to 3-4, the flat wire processing is performed by converting a round wire having a diameter φ (mm) before each flat wire processing into thickness t (mm) × width w (mm). Were processed by cold rolling into a rectangular wire of the size.
Table 3-4 shows the degree of processing in the final cold working (finish cold drawing) in the column of “Degree of processing in final processing”.

  Tables 1-1 to 1-3, 2-1 to 2-15, 3-1 to 3-5, and 4-1 to 4-3, the production conditions of the copper alloy wire according to the present invention and the copper alloy wire of the comparative example And the average crystal grain size of the base material and the area ratio of particles having <101> orientation are shown together with the properties of the obtained copper alloy wire. In addition, the area ratio of particles having <100> orientation or <111> orientation is shown.

[Characteristic]
Various characteristics were tested and evaluated for the round wire and flat wire samples obtained as described above.

  Tensile strength (TS) and elongation (El) were measured according to JIS Z2201 and Z2241, respectively, for the copper alloy wires after the final annealing. In the table, “tensile strength after heat treatment” and “elongation after heat treatment” are shown, respectively. A tensile strength of 260 MPa or more was judged acceptable. The elongation was judged to be 10% or more.

  The conductivity (EC) was measured according to JIS H0505. The electrical conductivity was evaluated as 70% IACS or higher, 80% IACS or higher as good, 90% IACS or higher as excellent, and less than 70% IACS as unacceptable.

  The average crystal grain size (GS) was measured by a cutting method (JIS G0551) from observation of a microstructure of a cross section (transverse section) perpendicular to the longitudinal direction of each sample wire. In each table, it was simply indicated as “crystal grain size”.

The crystal orientation of the recrystallized texture is EBSD (Electron BackScatter
Measurement and evaluation were carried out by the following method. The cross section perpendicular to the longitudinal direction of each copper alloy wire sample wire was scanned in steps of 0.02 μm, and the orientation of each crystal grain was observed and analyzed. For the analysis, analysis software OIM software (trade name) manufactured by TSL Solutions was used. As a result of the analysis, a plane whose deviation angle from the <101> orientation is within ± 10 degrees is defined as a <101> plane, and a cross section perpendicular to the longitudinal direction of each copper alloy wire sample is taken from the normal direction of the cross section. A crystal grain having a plane whose deviation angle from the <101> orientation is within ± 10 degrees when observed by the EBSD method is defined as a crystal grain having a <101> orientation. And the area ratio (%) of the crystal grain which has <101> orientation was calculated | required from the ratio with respect to the total measurement area of the area | region of the crystal grain which observed and measured in this way. In each table, <101> area ratio is indicated. The area ratio of particles having <100> orientation or <111> orientation was also determined in the same manner.

  The coil life was evaluated by performing the bending fatigue test using the apparatus shown in FIG. 2, measuring the number of bending fatigue fractures until the specimen of the copper alloy wire broke, and measuring the number of fractures. As shown in FIG. 2, a sample of a copper alloy wire having a wire diameter φ or a wire thickness t is sandwiched between dies as a sample, and a 20 g weight (W) is hung on the lower end to apply a load in order to suppress the deflection of the wire. It was. In the case of a flat wire, the sample was set so as to be sandwiched between dies in the wire thickness direction (ND). The upper end of the sample was fixed with a connector. In this state, the sample was bent 90 degrees to the left and right, repeatedly bent at a rate of 100 times per minute, and the number of bending until breaking was measured for each sample. The number of times of bending was counted as one round trip of 1 → 2 → 3 in the figure, and the interval between the two dies was set to 1 mm so as not to press the copper alloy wire sample during the test. The determination of breakage was made when the weight suspended at the lower end of the sample dropped. The bending radius (R) was set to 1 mm depending on the curvature of the die. The number of times of repeated bending until bending (number of bending fatigue breaks) was 2001 or more is “AA (particularly excellent)”, and the number of times of 100 to 2000 times or more is “A (excellent)”, 501 Those that were 1000 times were evaluated as “B (good)”, and those that were 500 times or less were evaluated as “D (poor)”.

  The coil formability was evaluated based on the frequency of disconnection per 100 km by testing the frequency of occurrence of disconnection when a sample of 100 km of a copper alloy wire was wound into a coil having a diameter of 3 mm (φ3 mm). “A (excellent)” when the occurrence frequency of the disconnection was 0 times or more and less than 0.3 times, “B (good)” when the occurrence frequency was 0.3 times or more and less than 0.6 times, 0.6 Those that were not less than 1.0 and less than 1.0 were evaluated as “C (possible)”, and those that were not less than 1.0 were evaluated as “D (poor)”.

  Comprehensive evaluation is "A (excellent)" which is excellent as a copper alloy wire for ultrafine wire coils at a low cost, judging from the tensile strength, elongation, electrical conductivity, and coil characteristics (coil life, coil formability). Then, “B (good)”, “C (good)”, and “D (poor)” were evaluated.

  In Tables 1-1 to 1-3, Cu-2% Ag alloy wires were processed and heat-treated so as to have a final wire diameter of 0.1 mm (φ0.1 mm). The result of having measured and evaluated the characteristic of the round wire sample (comparative examples 1-10) of a comparative example is shown.

  In each of Examples 1 to 10, since the processing and heat treatment conditions were appropriately adjusted so that the area ratio of the texture in the <101> orientation was 10% or more, the elongation was 25% or more and the strength was 300 MPa or more. All are high, and the conductivity, coil life and coil formability are also good. Particularly, in Examples 1 to 4 in which the final degree of work (η) in the final cold working before the final annealing is 0.5 or more and 2 or less, the area ratio of the <101> texture is 20% or more, and the elongation is 35. % And higher, and the coil formability is even better. Moreover, since the final work degree ((eta)) in the finish cold work before finish annealing was the value exceeding 3 and 4 or less, since Example 8 and 9 refined | miniaturized the crystal grain size to 0.1 micrometer, another Example Compared with, the elongation was not so high. Similarly, in Example 10, where the final annealing temperature was as high as 850 ° C., the elongation was not so high as compared with the other examples. For this reason, in these Examples 8, 9, and 10, compared with other Examples, the coil formability was not so high.

On the other hand, in Comparative Examples 1-6, since the final cold work degree was too large, the area ratio of <101> texture was small, and elongation and coil moldability were inferior. In Comparative Example 7, since the temperature of the final heat treatment was low in the semi-softening temperature range, the area ratio of the <101> texture was small, the strength was high and the coil life was excellent, but the elongation and the coil formability were inferior. In Comparative Example 8, since the degree of work (η) before intermediate annealing was too large exceeding 4, the texture of <111> orientation remained much, the area ratio of the texture of <101> orientation was small, and the elongation was Coil formability was inferior. In Comparative Example 9, since the intermediate heat treatment was insufficient, the processing strain could not be sufficiently removed and it was carried over to the next process. Therefore, the area ratio of <101> texture was small, and the elongation and coil formability were low. inferior. In Comparative Example 10, the degree of work before heat treatment was too high, and the temperature of intermediate annealing was high, so the crystal grains were coarsened, and the elongation and coil formability were inferior. These Comparative Examples 1 to 10 were all inferior in elongation and coil formability.
As described above, according to the present invention, the <101> texture can be controlled by appropriately controlling the heat treatment temperature and the degree of processing, and it has a higher level of strength and elongation, as well as coil characteristics. An excellent copper alloy wire can be obtained.

Tables 2-1 to 2-15 show examples and comparative examples of copper alloy round wires having various alloy compositions other than Cu-2% Ag alloy.
In the column of “Degree of processing in final processing” in the table, the final finish cold processing performed immediately before the final heat treatment x (xth, x = final) among “heat treatments 1 to 5”. The degree of processing at (xth, x = final) is shown.

  Also in the case of a copper alloy round wire in which at least one element selected from the group consisting of (1) Ag and / or (2) Sn, Mg, Zn, In, Ni, Co, Zr and Cr is added to Cu. As in the case of the -Ag alloy, by controlling the <101> texture amount to obtain the area ratio of crystal grains having a predetermined <101> orientation, the elongation, strength and conductivity are high, and the coil characteristics ( Coil life and coil formability were also excellent. Among these, the round wire of Cu-Ag alloy has higher strength than other copper alloy round wires. For example, when Examples 11 to 25 and Examples 26 to 43 that have been subjected to substantially the same processing and heat treatment are compared, Examples 11 to 25 are superior in characteristics, and the Cu—Ag alloy round wire is particularly suitable for a magnet wire. It turns out that it is.

Tables 3-1 to 3-5 show examples of flat wire rods and comparative examples.
In Table 3, the size after flat wire processing is indicated by thickness t (mm) × width w (mm). Of the “heat treatment 2, heat treatment 3 or heat treatment 4”, the rectangular wire processing is performed on the round wire of the diameter φ (mm) after the final intermediate heat treatment x (xth, x = final) “heat treatment 3”. , Heat treatment 4 or heat treatment 5 ”. The last heat treatment shown in the column of “Heat Treatment 3, Heat Treatment 4 or Heat Treatment 5” is the final heat treatment (final annealing).

  From Tables 3-1 to 3-5, even in the case of a flat wire, the same results as in the case of the round wires shown in Tables 1-1 to 1-3 and Tables 2-1 to 2-15 were obtained. I understand.

  Tables 4-1 to 4-3 show examples of the present invention and comparative examples of the round wire rods when the final wire diameter is swung from φ0.05 mm to 0.2 mm with a Cu-2% Ag alloy.

In the bending test, the bending radius R was fixed to 1 mm so that the bending strain was constant at any wire diameter. Compared to the comparative example, the copper alloy round wire of any wire diameter showed excellent characteristics in the example of the present invention and excellent coil characteristics. In particular, in the case of a copper alloy round wire having a thin wire diameter, the performance difference between the example of the present invention and the comparative example becomes more prominent, and it can be seen that the present invention is very effective with an extra fine wire.
In the case of a rectangular wire, the same result as in the case of the round wire is obtained.

  While the invention has been described in conjunction with the embodiments thereof, it is not intended that the invention be limited in any detail to the description unless otherwise specified, which is contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted widely.

  This application claims the priority based on Japanese Patent Application No. 2014-072611 for which it applied for a patent in Japan on March 31, 2014, and this is referred to here for the contents of this description. Capture as part.

Claims (8)

It is a copper alloy wire containing 0.1 to 4.0% by mass of Ag, with the balance being Cu and inevitable impurities,
Copper alloy whose area ratio of crystal grains having <101> orientation is 10% or more and 40% or less of the total measured area when a cross section perpendicular to the longitudinal direction of the wire is observed by the EBSD method from the normal direction of the cross section wire. The content of Ag is 0.1 to 4.0% by mass, and at least one selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr is 0.05 to 0.00%. It is a copper alloy wire containing 30% by mass, the balance being Cu and inevitable impurities,
Copper alloy whose area ratio of crystal grains having <101> orientation is 10% or more and 40% or less of the total measured area when a cross section perpendicular to the longitudinal direction of the wire is observed by the EBSD method from the normal direction of the cross section wire. At least one selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr is contained in an amount of 0.05 to 0.30% by mass, and the balance is made up of Cu and inevitable impurities. A copper alloy wire,
Copper alloy whose area ratio of crystal grains having <101> orientation is 10% or more and 40% or less of the total measured area when a cross section perpendicular to the longitudinal direction of the wire is observed by the EBSD method from the normal direction of the cross section wire. The copper alloy wire according to any one of claims 1 to 3, wherein an area ratio of crystal grains having the <101> orientation is 20% or more and 40% or less of a total measurement area.   The copper alloy wire according to any one of claims 1 to 4, wherein the base material has an average crystal grain size of 0.2 to 5.0 µm. A step of obtaining a rough drawn wire by melting and casting a copper alloy material containing 0.1 to 4.0% by mass of Ag and the balance being an alloy composition of Cu and inevitable impurities;
A process of obtaining a wire having a predetermined wire diameter by repeating cold working and intermediate annealing at a working degree η of 0.5 or more and 4 or less at least once in this order on the rough drawn wire;
Thereafter, the wire has a process of performing a final cold working and a final annealing in this order with a working degree η of 0.5 or more and 4 or less,
The intermediate annealing and the final annealing are both at 400 to 800 ° C. under an inert gas atmosphere if done in batch, and the recrystallization temperature or more on the 30 minutes to 2 hours of the copper alloy material, or, If carried out in continuous mode at 500 to 850 ° C. under an inert gas atmosphere, and the a heat treatment of 0.1 to 5 seconds on the recrystallization temperature or more of the copper alloy material, a copper alloy wire according to claim 1 Manufacturing method. The content of Ag is 0.1 to 4.0% by mass, and at least one selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr is 0.05 to 0.00%. A step of obtaining a rough drawn wire by melting and casting a copper alloy material containing 30% by mass and the balance providing an alloy composition consisting of Cu and inevitable impurities;
A process of obtaining a wire having a predetermined wire diameter by repeating cold working and intermediate annealing at a working degree η of 0.5 or more and 4 or less at least once in this order on the rough drawn wire;
Thereafter, the wire has a process of performing a final cold working and a final annealing in this order with a working degree η of 0.5 or more and 4 or less,
The intermediate annealing and the final annealing are both at 400 to 800 ° C. under an inert gas atmosphere if done in batch, and the recrystallization temperature or more on the 30 minutes to 2 hours of the copper alloy material, or, If carried out in continuous mode at 500 to 850 ° C. under an inert gas atmosphere, and the a heat treatment of 0.1 to 5 seconds on the recrystallization temperature or more of the copper alloy material, a copper alloy wire according to claim 2 Manufacturing method. At least one selected from the group consisting of Sn, Mg, Zn, In, Ni, Co, Zr and Cr is contained in an amount of 0.05 to 0.30% by mass, and the balance is made up of Cu and inevitable impurities. A step of obtaining a rough drawn wire by melting and casting a copper alloy material that gives an alloy composition of:
A process of obtaining a wire having a predetermined wire diameter by repeating cold working and intermediate annealing at a working degree η of 0.5 or more and 4 or less at least once in this order on the rough drawn wire;
Thereafter, the wire has a process of performing a final cold working and a final annealing in this order with a working degree η of 0.5 or more and 4 or less,
The intermediate annealing and the final annealing are both performed at 300 to 800 ° C. or 400 to 800 ° C. in the case of containing Zr in an inert gas atmosphere when performed in a batch mode , and in any case, the copper alloy material. recrystallization temperature than the 30 minutes to 2 hours, or, if performed in a continuous mode at 500 to 850 ° C. If containing 400 to 850 ° C. or Zr in an inert gas atmosphere, and the both cases a heat treatment of 0.1 to 5 seconds on the recrystallization temperature or more of the copper alloy material, manufacturing method of the copper alloy wire according to claim 3.

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